JP2014218050A - Aluminum-resin composite, aluminum insulated wire, flat cable and method for producing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite of aluminum and a resin having excellent adhesion properties between the metal and the resin and capable of dealing with a continuous production process such as a wire production process.SOLUTION: The aluminum-resin composite comprises: a metal made of aluminum or an aluminum alloy; a metal compound film formed on the metal and made of aluminum hydroxide and/or aluminum hydrous oxide; a silane based compound linked on the metal compound film; and an insulated coating resin joined with the above metal via the metal compound film and the silane based compound.

Description

  The present invention relates to a resin-aluminum composite used in electronic devices, home appliances, vehicle parts, vehicle-mounted products, etc., and has excellent adhesion properties between the metal and the resin, and can be used for continuous manufacturing processes such as electric wire manufacturing processes. The present invention relates to a method for producing a composite of aluminum and resin, and an insulated wire and a flat cable using the same.

  In recent years, the need to use aluminum as a conductor instead of conventional copper has been increasing with the aim of avoiding the risk of future rise in copper prices, ease of resource procurement, and weight reduction especially for in-vehicle use. Low adhesion is a major issue. That is, since the adhesive force between aluminum and the resin is low, when tension is applied to wind the aluminum wire coated with the resin, the interface breakdown between the aluminum and the resin occurs, and the insulating coating of the resin peels off. In order to wind the insulating coating so as not to peel off, it is necessary to wind at a low speed and with a low tension, resulting in a problem that the winding density is lowered.

  Conventionally, as a method for improving the adhesion between aluminum and resin, a method has been proposed in which aluminum is immersed in ammonia or hydrazine and then a thermoplastic resin such as polybutylene terephthalate resin is brought into contact with the metal by injection molding (Patent Document 1). This method is limited to a thermoplastic resin, and is limited to a contact method between a metal and a resin by injection molding. Therefore, a sufficient improvement in adhesion characteristics with aluminum cannot be expected for a thermosetting resin film such as polyamideimide and polyimide formed by coating a solution on the metal surface and then baking. Furthermore, since the aqueous ammonia solution is a strong alkali and hydrazine is a carcinogenic substance, development of a process that is more environmentally friendly and more environmentally friendly is required.

  Further, as a method for improving the adhesion between the resin and the aluminum alloy, a method has been proposed in which the aluminum surface is treated with a silane coupling agent having a functional group such as an epoxy group or an amino group, and the phenol resin is brought into contact (Patent Document 2). However, since the aluminum surface is hydrophobic, the wettability of the aqueous solution of the silane coupling agent is poor, so that the original characteristics of the silane coupling agent that has an effect of improving the adhesion cannot be sufficiently extracted.

  In addition, as a method for improving adhesion between aluminum and resin, a metal compound film is formed on the aluminum surface for thermoplastic resins such as acrylonitrile-butadiene-styrene copolymer (ABS) resin, polyphenylene sulfide resin (PPS), and nylon resin. Then, a method of performing aluminum surface treatment using a triazine thiol derivative (Patent Document 3) has been proposed. However, this method requires a treatment time of 15 minutes for forming the metal compound film, and further requires a long time treatment of 50 minutes in the liquid immersion and heat treatment steps for the treatment with the triazine thiol derivative. It was not possible to cope with the continuous processing steps required for the manufacture of strips and the like, and it was limited to batch manufacturing steps only, and the productivity was very poor.

  From these points, polyamide imide used for electronic equipment, home appliances, vehicle parts, vehicle-mounted products, polyimide, polyimide, etc. There is a demand for the development of adhesion improvement methods that can handle continuous processes.

International Publication No. 03/064150 JP 2009-126126 A Japanese Patent Application No. 2011-052292

  The present invention solves the above problems and relates to aluminum and composites with resins used for electronic devices, home appliances, vehicle parts, vehicle-mounted products, etc. It aims at providing the composite of aluminum and resin which can respond to a continuous manufacturing process, and the insulated wire and flat cable using the same.

In order to achieve the above-mentioned object, the following invention is provided.
(1) A metal composed of aluminum or an aluminum alloy, a metal compound film formed on the metal and composed of aluminum hydroxide and / or aluminum hydrated oxide, and a silane bonded on the metal compound film An aluminum-resin composite comprising: a metal compound; and an insulating coating resin bonded to the metal via the metal compound film and the silane compound.
(2) The aluminum / resin composite according to (1), wherein the metal compound film contains γ-AlO.OH which is a hydrated oxide.
(3) The aluminum / resin composite according to (1) or (2), wherein the insulating coating resin is a thermosetting resin and includes a polyimide resin and a polyamideimide resin.
(4) The silane compound is a silane coupling agent represented by the following general formula [1] or a compound represented by the following general formula [2] obtained by hydrolyzing the silane coupling agent. The aluminum / resin composite according to any one of (1) to (3).
X—R—Si—Y ₃ [1]
X—R—Si (OH) ₃ [2]
However, in the formulas [1] and [2], X is a group having a nitrogen atom, R is an alkylene group having 1 to 6 carbon atoms connecting X and a silicon atom, and in the formula [1], Y is a hydrolyzable alkoxy group having 1 to 3 carbon atoms bonded to a silicon atom (5) Y in the silane coupling agent represented by the general formula [1] is a methoxy group or an ethoxy group The aluminum / resin composite as described in (4) above.
(6) R in the silane coupling agent represented by the general formula [1] or the compound represented by the general formula [2] is an ethylene group (— (CH ₂ ) ₂ —) or a propylene group (— ( (2) The aluminum / resin composite according to (4) or (5), which is CH ₂ ) ₃ —).
(7) X in the silane coupling agent represented by the general formula [1] or the compound represented by the general formula [2] is an amino group or an imino group. The aluminum / resin composite according to any one of 6).
(8) The hydroxyl group of the silane compound is formed by dehydration condensation with a hydroxyl group present on the surface of the metal compound film. Aluminum / resin composite.
(9) The aluminum / resin composite according to (8), wherein cohesive failure occurs in the metal compound coating on the surface of the metal when the insulating coating resin of the aluminum / resin composite is peeled off. body.
(10) Bonding on a metal wire made of aluminum or an aluminum alloy, a metal compound film made of aluminum hydroxide and / or aluminum hydrated oxide formed on the surface of the metal wire, and the metal compound film An aluminum insulated electric wire comprising: the silane-based compound, an insulating coating that covers the metal wire via the metal compound coating and the silane-based compound.
(11) A conductor made of aluminum or an aluminum alloy, a metal compound film formed of aluminum hydroxide and / or aluminum hydrated oxide formed on the surface of the conductor, and a silane bonded on the metal compound film A flat cable comprising: a base compound; and an insulating coating resin layer sandwiching the conductor from both sides through the metal compound film and the silane compound.
(12) A step of forming a metal compound film by immersing a metal made of aluminum or an aluminum alloy in an aqueous triethanolamine solution, a step of bonding a silane compound on the metal compound film, and the metal compound film And a step of forming a resin on the metal via the silane compound, and a method for producing an aluminum / resin composite.
(13) The step of forming the metal compound film comprises immersing the metal in a triethanolamine aqueous solution at 40 to 100 ° C. for 5 to 45 minutes to form a hydrated oxide on the surface of the metal, γ-AlO.OH. The method for producing an aluminum / resin composite according to claim 11, wherein:
(14) A step of forming a metal compound film by immersing a metal wire made of aluminum or an aluminum alloy in a triethanolamine aqueous solution, a step of bonding a silane compound on the metal compound film, and the metal compound And a step of forming an insulating coating on the metal wire through the coating and the silane-based compound.
(15) A step of forming a metal compound film by immersing a conductor made of aluminum or an aluminum alloy in a triethanolamine aqueous solution, a step of bonding a silane compound on the metal compound film, and a plurality of resin layers And sandwiching the conductor, and joining the conductor to the resin layer via the metal compound film and the silane compound.
(16) By using the aluminum / resin composite according to any one of (1) to (8), when the insulating coating resin is peeled from the aluminum / resin composite, the surface of the metal is A method for improving the peel strength of an aluminum / resin composite, wherein the peel strength of the composite is improved by causing cohesive failure in a metal compound coating.

  The present invention relates to a composite of aluminum and resin, and provides a composite of aluminum and resin that enhances adhesion characteristics between the metal and the resin and is compatible with a continuous manufacturing process such as an electric wire manufacturing process. The composite insulated wire and flat cable used, and the manufacturing method thereof can be provided.

Sectional drawing which shows the aluminum resin composite which concerns on embodiment of this invention. The aluminum resin composite manufacturing process which concerns on embodiment of this invention. The surface state change accompanying the manufacturing process of the aluminum resin composite which concerns on embodiment of this invention. (A) Hydration treatment (b) Silane compound treatment (c) Dehydration condensation reaction after silane compound treatment (d) Resin formation Sectional drawing which shows the aluminum insulated wire 11 which concerns on embodiment of this invention. Sectional drawing which shows the flat cable 21 which concerns on embodiment of this invention. The enlarged view of A part in FIG. Conceptual diagram of interface debonding mode for materials according to comparative example Conceptual diagram of interfacial debonding mode of material according to the present invention (cohesive failure)

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
As shown in FIG. 1, the aluminum / resin composite 1 includes a metal 3, a metal compound film 5 provided on the surface of the metal 3, a silane compound 7 provided on the metal compound film 5, and a silane compound. 7 has a resin 9 provided thereon. The metal 3 is made of aluminum or an aluminum alloy. The metal compound coating 5 is made of aluminum hydroxide and / or aluminum hydrated oxide. The resin 9 is an insulating resin, and a thermosetting resin is preferable depending on the purpose of use. As shown in FIG. 2, the aluminum / resin composite 1 is mainly formed by four steps of a cleaning treatment 101, a hydration treatment 102, a silane compound treatment 103, and a resin formation 104. Each process will be described below.

<Cleaning process>
The surface of the metal 3 made of aluminum or an aluminum alloy becomes non-uniform due to segregation and oxide film generated in the manufacturing process, or the rolling oil, cutting oil, press oil, etc. used during processing and molding adhere to it, It may become dirty due to rusting or fingerprints. For this reason, depending on the state of the surface of the metal 3, it is preferable to perform a cleaning process using an appropriate cleaning method.
Cleaning methods include physical methods such as grinding, buffing, and shot blasting, for example, electrochemical methods in which electrolytic treatment is performed in an alkaline degreasing liquid and cleaning is performed using generated hydrogen and oxygen, alkaline solvents A chemical method using (cleaning agent) can be used. Then, it is preferable to perform the post-process by an acidic liquid as a neutralization process.

<Hydration treatment>
The metal compound film 5 includes a hydroxide or a hydrated oxide. As shown in FIG. 3A, by performing a hydration treatment, a hydroxyl group is formed on the surface of the metal 3, and a metal compound film 5 containing a hydroxide or a hydrated oxide can be formed. Although it does not specifically limit as a method of forming this hydroxide or hydrated oxide, For example, it is larger than pH7 like water (pure water) or 0.3-0.5% triethanolamine aqueous solution, and is 12 or less. There is a method in which a weak alkaline aqueous solution (so-called boehmite treatment solution) is used and heated to 40 ° C. or higher (preferably 60 ° C. or higher), and the aluminum alloy is immersed in the heated water or weak alkaline aqueous solution. In order to efficiently form a hydroxyl group by a hydration reaction, the hydration solution is more preferably weakly alkaline. In addition, there is a treatment method in which an aluminum alloy is exposed to pressurized steam.

In the present invention, preferable conditions for the hydration treatment are as follows. A hydration treatment liquid in which at least one of an amine and an amide-based substance is added as an additive to pure water and the pH is adjusted to about 10 to 12 is used. An example of a preferable hydration treatment solution is a 0.5 vol% triethanolamine aqueous solution, and its pH is about 10. Processing temperature becomes like this. Preferably it is the range of 40-100 degreeC, More preferably, it is 60-90 degreeC. Within this range, it is possible to obtain a dense metal compound film 5 in a relatively short time. The treatment time is preferably 1 to 120 minutes, more preferably 5 to 45 minutes.
By performing this hydration treatment, a metal compound film 5 mainly composed of aluminum and a metal hydrated oxide contained in the aluminum alloy is formed on the surface of the aluminum alloy. In many cases, the metal compound film formed by this treatment is γ-AlO.OH which is a hydrated oxide or a non-porous film mainly composed of γ-AlO.OH and α-Al ₂ O _3. is there. The hydrated oxide γ-AlO.OH is also called oxyhydroxide. By these treatments, a relatively uniform metal compound film 5 having a film thickness of 0.02 to 10 μm, more preferably 0.05 to 2 μm can be formed.

Such a hydration treatment can form a metal compound film containing γ-AlO · OH as the main component, that is, it can form OH groups densely and uniformly on the surface of the aluminum substrate, and many fine irregularities are formed on the surface. Since this increases the contact surface area, it is effective for improving the bonding strength and is preferable as the hydration treatment according to the present invention.
The surface characteristics of the aluminum are greatly changed by the hydration treatment. For example, by immersing an aluminum alloy in a 0.5% triethanolamine aqueous solution at 80 ° C. for 30 minutes, the formation of a superhydrophilic surface with a water contact angle of 5 ° or less was confirmed. = 95 °) and the degreased / acid-treated surface (contact angle = 28 °), it can be confirmed that the hydrophilization is greatly advanced.

<Silane compound treatment>
The silane compound 7 used in the present invention includes a silane coupling agent represented by the following general formula [1] or a compound represented by the general formula [2] obtained by hydrolyzing the silane coupling agent.
X—R—Si—Y ₃ [1]
X—R—Si (OH) ₃ [2]

X in the silane coupling agent of the general formula [1] and the compound of the general formula [2] is a group having a nitrogen atom, and this group having a nitrogen atom forms the resin 9 on the silane compound 7. At this time, since it has an affinity with the polyamideimide or polyimide thermosetting resin forming the resin 9, the adhesion is remarkably improved. Examples of such X include an amino group, an imino group, and an isocyanate group. Among these, an amino group (—NH ₂ ) and an imino group (—NH—) having a structure in which a nitrogen atom is present in the vicinity of the end of X. ) Is preferred.
R is an alkylene group having 1 to 6 carbon atoms connecting X and a silicon atom, and preferably 2 or 3 carbon atoms. An ethylene group (— (CH ₂ ) ₂ —) or a propylene group (— (CH ₂ ) ₃ —) is particularly preferable.
Y at a position opposite to X is a hydrolytic C1-C3 alkoxy group bonded to a silicon atom, and is particularly preferably a methoxy group and / or an ethoxy group.
The Y or OH group is subjected to heat treatment or the like after a solution containing the silane coupling agent represented by the general formula [1] or the compound represented by the general formula [2] is applied on the surface of the metal compound, and the like. (B) As shown in FIG. 3C, an OH group present on the surface of the metal compound causes a dealcoholization condensation reaction or a dehydration condensation reaction. This reaction improves the adhesion between the metal compound and the silane compound.
In consideration of the reactivity with the OH group on the surface of the metal compound, the compound represented by the general formula [2] obtained by hydrolyzing the silane coupling agent represented by the general formula [1] is a silane compound. 7 is preferably formed.

  By treating the surface of the aluminum metal compound with a silane compound, the wettability of the aqueous silane coupling agent solution on the aluminum surface is greatly improved. In addition, the silane coupling agent adsorption unevenness can be clearly seen on the metal surface that has just been degreased and acid-treated, whereas the hydration-treated aluminum metal compound surface has no uneven adsorption. Therefore, it is considered that the adhesion improving properties of the original silane coupling agent can be sufficiently brought out.

<Resin formation>
As shown in FIG. 1, a resin 9 is formed on the upper layer of the silane compound 7. In the present invention, the thermosetting resin used for the resin material is preferably a resin having heat resistance and insulation. For example, polyimide, polyamide imide, polyester imide, polyether imide, polyamide, formal, polyurethane, polyester, polyvinyl formal, epoxy, polyhydantoin, and preferably excellent in heat resistance, polyimide, polyamide imide, polyester imide, polyether Polyimide resins such as imide and polyimide hydantoin-modified polyester. Moreover, these may be used individually by 1 type, and may mix and use 2 or more types.
In particular, when a silane coupling agent of the general formula [1] and a compound of the general formula [2] are used as the silane compound, X is a group having a nitrogen atom, and the group having a nitrogen atom is a polyimide-based compound Since the resin 9 has an affinity, when the resin 9 is a polyimide resin, the adhesion between the metal 3 and the resin 9 can be remarkably improved.

<Aluminum insulated wire>
The aluminum-resin composite according to the embodiment of the present invention can be used as an aluminum insulated wire. As shown in FIG. 4, the aluminum insulated wire 11 includes a metal wire 13 made of aluminum or an aluminum alloy, and an aluminum hydroxide and / or aluminum hydrate formed on the surface of the metal wire 13. A metal compound film 15 containing an oxide, a silane compound 17 bonded on the metal compound film 15, and an insulating film 19 that covers the metal wire 13 through the metal compound film 15 and the silane compound 17. . That is, the aluminum insulated wire 11 forms the aluminum / resin composite 1 according to the embodiment of the present invention at the interface between the metal wire 13 and the insulating coating 19. The metal wire 13 corresponds to the metal 3, the metal compound film 15 corresponds to the metal compound film 5, the silane compound 17 corresponds to the silane compound 7, and the insulating film 19 corresponds to the resin 9, and the same material can be used. . A coil can be produced by winding such an aluminum insulated wire 11. Since the aluminum insulated wire 11 has good adhesion between the metal wire 13 and the insulating coating 19, it can be wound at a high rotational speed with a strong tension, and a coil with a high winding density can be obtained with high productivity. it can.

<Flat cable>
As shown in FIG. 5, the flat cable 21 according to the embodiment of the present invention has a configuration in which a conductor 23 made of aluminum or an aluminum alloy is sandwiched between a resin layer 29 and a resin layer 31 from both sides. FIG. 6 is an enlarged view of portion A in FIG. As shown in FIG. 6, the flat cable 21 includes a conductor 23 made of aluminum or an aluminum alloy, a metal compound film 25 containing aluminum hydroxide and / or aluminum hydrated oxide formed on the surface of the conductor 23, and A silane compound 27 bonded on the metal compound film 25 and resin layers 29 and 31 sandwiching the conductor 23 from both sides through the metal compound film 25 and the silane compound 27 are provided. That is, the flat cable 21 forms the aluminum / resin composite 1 according to the embodiment of the present invention at the interface between the conductor 23 and the resin layer 29 or the resin layer 31. The conductor 23 corresponds to the metal 3, the metal compound coating 25 corresponds to the metal compound coating 5, the silane compound 27 corresponds to the silane compound 7, and the resin layers 29 and 31 correspond to the resin 9. it can. Such a flat cable 21 can be used for wiring of an electric machine. Since the flat cable 21 has good adhesion between the conductor 23 and the resin layers 29 and 31, peeling does not occur between the conductor 23 and the resin layers 29 and 31 even when bending is repeated.

<Effects according to this embodiment>
In the present embodiment, by hydrating the surface of the metal 3, the hydrated oxide can be densely and uniformly formed on the surface of the aluminum or aluminum alloy substrate, and many fine irregularities are formed on the surface. , The contact surface area can be increased. As a result, the bonding strength between the metal 3 and the resin 9 can be improved.
In this embodiment, the adhesion between the silane compound 7 and the metal compound film 5 can be improved by a dehydration condensation reaction between the silanol of the silane compound 7 and the hydroxyl group on the surface of the metal compound film 5.
In particular, when a silane coupling agent of the general formula [1] and a compound of the general formula [2] are used as the silane compound, X is a group having a nitrogen atom, and the group having a nitrogen atom is a polyimide-based compound Since the resin 9 has an affinity for the resin, the adhesion between the metal 3 and the resin 9 can be remarkably improved when the resin 9 is a polyimide resin. Characteristics can be improved.

  Furthermore, since the manufacturing method of the composite body of aluminum and resin in this embodiment can be processed in a short time compared with the past, it is applicable to continuous manufacturing processes, such as an electric wire manufacturing process.

  Next, in order to further clarify the effects of the present invention, examples and comparative examples will be described in detail, but the present invention is not limited to these examples.

<Example 1>
1. Surface treatment was performed in the following order using an aluminum surface-treated aluminum alloy (A1N30H, thickness = 100 μm).
1-1. Washing treatment (1) Degreasing treatment: immersed in a sodium hydroxide solution (10 g / L, room temperature, 400 A / m ² ) for 30 seconds (2) Washing with water: ion-exchanged water (resistivity = 18.0 Ω · cm, Millipore Corp. (3) Neutralization (acid) treatment: immersion in nitric acid (100 g / L) for 30 seconds (4) Washing in water: immersion in ion-exchanged water for 30 seconds 1-2. Hydration treatment (1) Hydration treatment: Immersion in 80 ° C. triethanolamine aqueous solution (0.5 wt.%) For 30 minutes (2) Washing in water: Immersion in ion-exchanged water for 30 seconds 1-3. Silane-based compound treatment (1) Silane-based compound treatment: aminosilane (3-aminopropyltriethoxysilane, manufactured by Momentive, A1100) immersed in a 1 vol% aqueous solution at room temperature for 30 seconds (2) dried and heat-treated in a constant temperature hot air bath (100 ° C, 1 minute)
2. Resin formation on aluminum surface Polyamideimide (PAI, HI406SA) resin was uniformly coated on the aluminum surface of the above treatment using a coater (resin thickness = about 10 μm). Thereafter, heat treatment was performed for 20 minutes at 150 ° C., 200 ° C., and 250 ° C., and the resin on the metal surface was baked.

<Example 2>
A test piece was prepared in the same manner as in Example 1 except that a 40 ° C. triethanolamine aqueous solution (0.5 wt.%) Was used as the hydration treatment condition.

<Example 3>
A test piece was prepared in the same manner as in Example 1 except that a 60 ° C. triethanolamine aqueous solution (0.5 wt.%) Was used as the hydration treatment condition.

<Example 4>
As an hydration treatment condition, an aluminum test piece was prepared in the same manner as in Example 1 except that the aluminum test piece was immersed in an aqueous triethanolamine solution (0.5 wt.%) At 80 ° C. for 5 minutes.

<Example 5>
As an hydration treatment condition, an aluminum test piece was prepared in the same manner as in Example 1 except that the aluminum test piece was immersed in an aqueous triethanolamine solution (0.5 wt.%) At 80 ° C. for 10 minutes.

<Example 6>
As an hydration treatment condition, an aluminum test piece was prepared in the same manner as in Example 1 except that the aluminum test piece was immersed in an aqueous triethanolamine solution (0.5 wt.%) At 80 ° C. for 20 minutes.

<Comparative Example 1>
A test piece subjected to only the cleaning treatment of Example 1 was prepared.

<Comparative example 2>
After the cleaning treatment of Example 1, a test piece was prepared in the same manner as in Example 1 except that the aluminum test piece was immersed in an aqueous ammonia solution (14 vol%) at 25 ° C. for 30 minutes.

<Comparative Example 3>
After the cleaning treatment of Example 1, an aluminum test piece was immersed in 1 vol% aqueous solution of aminosilane (3-aminopropyltriethoxysilane, APTES, manufactured by Momentive, A1100) at room temperature for 30 seconds in the same manner as in Example 1. A test piece was prepared.

<Comparative example 4>
A test piece was prepared in the same manner as in Example 1 except that a resin coat was formed without performing the silane compound treatment.

<Comparative Example 5>
A test piece was prepared in the same manner as in Example 1 except that a 1 vol% aqueous solution of a silane compound having a thiol functional group (A189, manufactured by Momentive) was used as the silane coupling agent. This corresponds to the manufacturing method described in Patent Document 3.

(Evaluation of test piece adhesion)
A 90 ° peel test was conducted to evaluate the adhesion between metal and resin. The adhesion was evaluated by pulling the resin side at a peel speed of 10 mm / min (Shimadzu Auto Club, AG-10 kNI) and measuring the stress at that time. The test results are shown in the table.

  As is clear from Tables 1 and 2, in Examples 1 to 6, a high adhesion force of 600 N / m or more was confirmed, and a clear improvement in characteristics was confirmed compared to the untreated product (Comparative Example 1). On the other hand, it can be seen that the conventional ammonia-treated product (Comparative Example 2) and the thiol group-containing silane compound-treated product (Comparative Example 5) do not provide significant improvement in adhesion properties. In particular, in Example 4, it can be seen that sufficient adhesion can be obtained even if the hydration treatment is completed in a short time.

  7 and 8 are conceptual diagrams of the interface peeling mode between the material according to the comparative example and the material according to the example. Here, FIG. 7 shows the conceptual diagram of the interface peeling mode in a comparative example, and FIG. 8 shows the conceptual diagram of the interface peeling mode in an Example. Here, in FIG. 7, in the untreated Comparative Example 1, peeling occurred at the interface between the metal 51 and the resin 53 when the resin 53 peeled off during the adhesion evaluation. Similarly, in Comparative Examples 2 to 5, peeling occurred at any interface between the resin and the metal when the resin peeled off during the adhesion evaluation. However, in Examples 1 to 6, as shown in FIG. 8, breakage occurred in the metal compound film 5 of the hydrated metal 3 and peeling occurred. That is, in Examples 1-6, it turned out that the peeling behavior has changed a lot compared with the comparative example.

  The analysis results of the peeling interface in the comparative example and the example were obtained by analyzing the peeling interface between the metal and the resin by X-ray photoelectron spectroscopy (XPS). In the case of the comparative example in which (FIG. 7) is confirmed, the cause is considered to be that the interaction between the metal 51 and the resin 53 is weak and the bonding force at the interface is low. On the other hand, in the example in which the cohesive failure (FIG. 8) was confirmed in the metal compound film 5 as the peeling behavior, the interaction at the interface between the metal and the metal hydroxide, the resin and the silane coupling agent was strong. As a result of increasing the bond strength at each of the interfaces, it is considered that cohesive failure occurred in the metal compound film 5 that is an aluminum hydroxide layer instead of interface failure as a peeling behavior. It can be judged that a high adhesion strength can be obtained by a simple mechanism.

  Moreover, in the conventional electric wire which uses copper as a conductor, the adhesive force of polyamideimide resin and copper is about 400 N / m. Furthermore, since aluminum is more easily stretched than copper, it cannot be wound with the same tension unless the adhesion between aluminum and resin is higher than the adhesion between copper and resin. In Examples 1-6, since it has high adhesive force, even if it winds by high tension, the resin film is not destroyed and the winding wound at high density can be obtained.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to the example which concerns. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea disclosed in the present application, and these are naturally within the technical scope of the present invention. Understood.

1 ......... Aluminum / resin composite 3 ......... Metal 5 ......... Metal compound coating 7 ......... Silane compound 9 ...... Resin 11 ...... Aluminum insulated wire 13 ......... Metal wire 15 ......... Metal compound coating 17 ......... Silane compound 19 ......... Insulation coating 21 ......... Flat cable 23 ......... Conductor 25 ......... Metal compound coating 27 ......... Silane compound 29 ......... Resin layer 31 ... ... Resin layer 51 ... Metal 53 ... …… Resin

Claims (16)

  A metal made of aluminum or an aluminum alloy, a metal compound film formed on the metal and made of aluminum hydroxide and / or an aluminum hydrated oxide, and a silane compound bonded on the metal compound film; An aluminum-resin composite comprising: an insulating coating resin bonded to the metal via the metal compound film and the silane compound.   The aluminum / resin composite according to claim 1, wherein the metal compound coating contains γ-AlO.OH which is a hydrated oxide.   The aluminum / resin composite according to claim 1 or 2, wherein the insulating coating resin is a thermosetting resin and includes a polyimide resin and a polyamideimide resin. The silane compound is a silane coupling agent represented by the following general formula [1] or a compound represented by the following general formula [2] obtained by hydrolyzing the silane coupling agent. Item 4. The aluminum / resin composite according to any one of Items 1 to 3.
X—R—Si—Y ₃ [1]
X—R—Si (OH) ₃ [2]
However, in the formulas [1] and [2], X is a group having a nitrogen atom, R is an alkylene group having 1 to 6 carbon atoms connecting X and a silicon atom, and in the formula [1], 4. The aluminum / resin composite according to claim 3, wherein Y is a hydrolyzable alkoxy group having 1 to 3 carbon atoms bonded to a silicon atom.   The aluminum / resin composite according to claim 4, wherein Y in the silane coupling agent represented by the general formula [1] is a methoxy group or an ethoxy group. R in the silane coupling agent represented by the general formula [1] or the compound represented by the general formula [2] is an ethylene group (— (CH ₂ ) ₂ —) or a propylene group (— (CH ₂ )). ₃ -) aluminum resin complex according to claim 4 or 5, characterized in that a.   X in the silane coupling agent represented by the general formula [1] or the compound represented by the general formula [2] is an amino group or an imino group. 2. The aluminum / resin composite according to item 1.   The aluminum / resin composite according to any one of claims 1 to 7, wherein the hydroxyl group of the silane compound is formed by dehydration condensation with a hydroxyl group present on the surface of the metal compound film. .   9. The aluminum / resin composite according to claim 8, wherein cohesive failure occurs in the metal compound coating on the surface of the metal when the insulating coating resin of the aluminum / resin composite is peeled off.   A metal wire made of aluminum or an aluminum alloy, a metal compound film made of aluminum hydroxide and / or aluminum hydrated oxide formed on the surface of the metal wire, and a silane system bonded on the metal compound film An aluminum insulated wire comprising: a compound; and an insulating coating that covers the metal wire through the metal compound coating and the silane compound.   A conductor made of aluminum or an aluminum alloy, a metal compound film formed of aluminum hydroxide and / or aluminum hydrated oxide, and a silane compound bonded on the metal compound film, formed on the surface of the conductor; A flat cable comprising: an insulating coating resin layer sandwiching the conductor from both sides with the metal compound film and the silane compound interposed therebetween.   A step of forming a metal compound film by immersing a metal comprising aluminum or an aluminum alloy in an aqueous solution of triethanolamine, a step of bonding a silane compound on the metal compound film, the metal compound film and the silane And a step of forming a resin on the metal via a system compound, and a method for producing an aluminum / resin composite.   In the step of forming the metal compound film, the metal is immersed in a triethanolamine aqueous solution at 40 to 100 ° C. for 5 to 45 minutes to form γ-AlO.OH that is a hydrated oxide on the surface of the metal. The method for producing an aluminum / resin composite according to claim 12. A step of forming a metal compound film by immersing a metal wire made of aluminum or an aluminum alloy in a triethanolamine aqueous solution, a step of bonding a silane compound on the metal compound film, the metal compound film and the Forming an insulating film on the metal wire via a silane compound;
The manufacturing method of the aluminum insulated wire characterized by comprising.   A step of forming a metal compound film by immersing a conductor made of aluminum or an aluminum alloy in a triethanolamine aqueous solution, a step of bonding a silane compound on the metal compound film, and a plurality of resin layers And a step of joining the conductor to the resin layer via the metal compound film and the silane compound. The metal compound coating on the surface of the metal when the insulating coating resin is peeled off from the aluminum / resin composite by using the aluminum / resin composite according to any one of claims 1 to 8. A method for improving the peel strength of an aluminum / resin composite, wherein the peel strength of the composite is improved by causing cohesive failure in the inside.

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